Pesticidal preparation containing aromatic phosphoric or phosphonic acid esters



United States Patent ()flice 3,538,221 Patented Nov. 3, 1970 3,538,221 PESTICIDAL PREPARATION CONTAINING ARO- MATIC PHOSPHORIC R PHOSPHONIC ACID ESTERS Ernst Beriger, Allschwil, Switzerland, assignor to Ciba Limited, Basel, Switzerland, a company of Switzerland No Drawing. Original application Nov. 16, 1965, Ser. No. 508,157. Divided and this application Dec. 26, 1968, Ser. No. 798,559 Claims priority, application Switzerland, Nov. 20, 1964, 14,977/64 Int. Cl. A01n 9/36 U.S. Cl. 424225 6 Claims ABSTRACT OF THE DISCLOSURE This invention relates to methods and pesticidal preparation for treating plants to protect them from pests such as insects and fungi.

This application is a division of Ser. No. 508,157, filed Nov. 16, 1965.

The present invention relates to new aromatic phosphoric or phosphonic acid esters of general formula in which R represents a low alkyl, alkoxy or alkylthio group, a low halogenoalkyl group or an aryl group, R denotes methyl or ethyl, and X and Y independently of one another denote oxygen or sulphur atoms.

The phosphoric or phosphonic acid esters defined by Formula I have insecticidal, fungicidal, acaricidal, nematocidal and molluscicidal properties.

In the formula given above, R may represent an alkoxy or alkylthio group; such groups are for example: methoxy, methylthio, ethoxy, ethylthio, propoxy, propylthio, isopropoxy and isopropylthio.

In the formula given above R may, according to the definition, further represent a low alkyl group, for example, methyl, ethyl or isopropyl. Furthermore, R may, according to the definition, denote a halogenoalkyl group, for example, halogenomethyl such as chloromethyl or bromomethyl. However, higher alkylated groups are also possible, as for example a-halogenoethyl or a-halogeno propyl groups.

According to the definition, R may also represent an aryl group, for example phenyl or substituted phenyl, preferably halogen-substituted phenyl for example, 2,4- dichloroor 2,4-dibromo-phenyl. The phenyl group R may, in addition to halogen atoms, contain further substituents, for example low alkyl groups such as tert. butyl or tert. amyl groups, nitro groups or trifluoromethyl groups.

The new phosphoric or phosphonic acid esters of Formula I may be used in numerous types of pesticides.

The present invention therefore also provides pesticides in which the active substance is at least one of the phosphoric or phosphonic acid esters of Formula I of the invention, optionally with other additives for example, carriers, solvents, diluents, dispersing agents, adhesives, Wetting agents, fertilizers, and under certain circumstances other pesticides.

As a result of their wide biocidal action, the new agents havethe particular advantage that they may be used to combat very varied types of animal pests.

They are therefore not only siutable as insecticides but also show outstanding action against harmful microorganisms, for example, against fungi such as Alternaria solanz', Phwtopthora infestans and Septoria apii, as well as against harmful acarides, nematodes and their eggs or larvae, when used for plant protection at a concentration which does not cause any phytotoxic phenomena. Furthermore, the new materials are generally usuable as microbiocides, for example against varieties of Aspergillus, as well as insecticides, for example, against midges and flies.

In order to produce directly sprayable solutions of compounds of general Formula I, there may be used, for example, mineral oil fractions of high to medium boiling range for example diesel oil or kerosene, coal tar oil and oils of vegetable or animal origin, as well as hydrocarbons for example, alkylated napthalenes, tetrahydroanaphthalene, optionally with the use of xylene mixtures, cyclohexanols, ketones and also chlorinated hydrocarbons for example, trichlorethane, trichlorethylene or triand tetrachlorobenzenes, It is advantageous to use organic solvents having a boiling point of above C. Aqueous application forms are especially advantageously prepared from emulsion concentrates, pastes or wettable spray powders, by the addition of water. As emulsifying or dispersing agents, there may be used nonionic products, for example, condensation products of aliphatic alcohols, amines or carboxylic acids having a long-chain hydrocarbon group of about 10 to 20 carbon atoms, with ethylene oxide, for example, the condensation product of octadecyl alcohol and 25 to 30 mols of ethylene oxide, or that of soya bean fatty acid and 30 mols of ethylene oxide, or that of technical grade oleylamine and 15 mols of ethylene oxide, or that of dodecylmercaptan and .12 mols of ethylene ox ide. Amongst anionic emulsifying agents which may be used, one may mention: the sodium salt of the sulfphate ester of dodecyl alcohol, sodium dodecylbenzene-sulphonate, the potassium or triethanolamine salt of oleic or abietic acid or of mixtures of these acids, or the sodium salt of a petroleum sulphonic acid. Cationic dispersing agents that may be used are quaternary ammonium compounds for example cetyl-pyridinium bromide, or dioxethylbenzyldodecylammonium chloride.

Talc, kadin, bentonite, calcium carbonate, and also charcoal, cork meal, wood meal and other materials of vegetable origin may be used as solid carriers for the preparation of dusting and sprinkling agents. The production of the preparations in a granular form is also very useful. The various forms of application may contain, in the usual Way, additives to improve the distribution, adhesion, resistance to rain or the penetrating power. As such materials there may be mentioned fatty acids, resins, glue, casein or alginates.

The materialsof the invention may be used by themselves or together with conventional pesticides, especially insecticides, acaticides, nematocides, bactercides or other fungicides.

The invention further provides a process for the preparation of the new phosphoric or phosphonic acid esters of Formula I, which comprises reacting a phosphoric acid or phosphonic acid halide of formula RIX RZY n in which R R Y and X have the meanings given above, and Hal represents a halogen atom, preferably chlorine, with a metal salt, preferably the sodium salt of 2,5-dichloro-4-iodophenol.

The process may be carried out in the presence or absence of solvents; solvents which may be used are for example benzene, toluene, xylene and chlorobenzene.

Most of the esters obtainable according to the invention are oily, but some are crystalline low-melting substances.

These are generally easily soluble in ethanol and acetone. The 2,5-dichloro-4-iodophenol used as the starting material may be prepared as follows: 81.5 parts of 2,5-dichlorophenol are neutralised with 20.5 parts of sodium hydroxide in 1000 parts of water. A solution of 127 parts of iodine in 127 parts of potassium iodide and 500 parts of water is added dropwise to this solution during 1 hour, at to The mixture is then stirred for a further 1 hour at room temperature and thereafter a solution of 100 parts of concentrated sulphuric acid in 200 parts of ice is added, parts of sodium bisulphite are added to this, and the precipitated 2,5-dichloro-4-iodophenol is filtered off and recrystallised from cyclohexane. 113 parts by weight of the pure compound, melting at 74 C., are obtained.

The following examples illustrate the invention:

EXAMPLE 1 28.9 parts of 2,5-dichloro-4-iodophenol are stirred with 16 parts of potassium carbonate and 0.5 part of copper powder in 75 parts by volume of methyl ethyl ketone. 18.9 parts of diethyl thiochlorophosphate are added dropwise to this mixture during 15 minutes, and the mix then heated to 7080 C. for a further 8 hours. After cooling, the solid components are filtered off and the filtrate evaporated in vacuo at 50. The residue is dissolved in 100 parts by volume of methylene chloride and washed twice with 25 parts by volume of ice-cooled caustic soda at a time. The methylene chloride solution is dried over sodium sulphate and the solvent evaporated off in vacuo at 50. The residue obtained consists of 28 parts of the condensation product in the form of a reddish-coloured oil which solidifies to crystals after standing for a while. These melt at 4748 C. after recrystallization from methanol. The

EXAMPLE 2 24 parts of 2,5-dichloro-4-iodophenol are dissolved in 100 parts of water by means of 3.4 parts of sodium hydroxide. The water is removed in vacuo and the dried sodium salts dissolved in 100 parts by volume of toluene.

The solution is warmed to 7080 and 15 parts of dimethyl thiochlorophosphate are added dropwise. The mixture is stirred for a further 8 hours at 70-80". After cooling the salt is filtered off, and the solution successively washed with water and 1 N ice-cooled caustic soda. The solution is dried over sodium sulphate and the solvent is evaporated off in vacuo, at 50 bath temperature. The residue obtained consists of 24 parts of the condensation product in the form of a pale yellow oil.

This solidifies, after standing for a while, to crystals melting at 72 to 73.

The condensation product has the following formula 01 CHaO S l The following esters may be prepared in the same manner as that described in Examples 1 and 2:

EXAMPLE 9 (DUSTING POWDER) 2 parts of one of the active substances of Examples 1 to 8 are sprayed on to 98 parts of kaolin and the mixture obtained ground to a homogeneous dust.

EXAMPLE 10 (WETTABLE POWDER) 25 parts of one of the active substances of Examples 1 to 8 are sprayed on to 73 parts of kieselghur and the whole mixture subsequently ground with 2 parts of naphthalene-sulphonic acid to form a homogeneous mass. Water is added to this mass until the desired concentration of active substance is reached.

EXAMPLE 11 (EMULSION) 20 parts of one of the active substances of Examples 1 to 8 are dissolved in 75 parts of xylene and 5 parts of castor oil butyl ester sulphonate are added.

The solution so obtained is suspended in an amount of water such that the desired concentration of active substance is obtained.

EXAMPLE 12 The esters of Examples 1 and 2 were compared as to their bait poison effect on Prodenia, with the 0,0-dimethyl thiophosphoric acid 2,5-dichloro-4-bromophenyl ester (cf. French Pat. No. 1,344,586) commercially available under the generic name Bromophos. In the course of this, the following results were obtained:

Mortality in percent Gone. percent ac- Bromophos Example 1 Example 2 tive Substance clleet after days 1 2 4 1 2 4 1 2 4 1 New population, where 100% have been killed.

It is surprising that such an increase in effectiveness could be achieved, particularly at low concentrations, by replacing the bromine by an iodine atom; such an increase in effectiveness could not be foreseen.

EXAMPLE 13 Aphids on string beans were treated, in an open field experiment, with the compounds according to Examples 1 and 2, formulated according to Example 11. The comparison substance used was 2 isopropyl-4-methyl-pyri-midyl-6-0-0-diethyl-thiophosphoric acid ester. (Referred to as Compound V in the following examples.)

, -The following results were obtained:

Number of aphids 3 days 3 days before after treattreet- Compound ment ment EXAMPLE 14 Macrosiphon rosae on roses were treated with the compounds of Examples 1 and 2.

Number of aphids 3 days 3 days before after treattreat- Compound ment ment ount used in ercent:

Am f Control untreated..- 270 270 0.03 Example 1 1, 400 0 0.03 Example 2 540 0 0.025 CompoundV 320 0 EXAMPLE Larvae of Psylla mzzli on apple trees were sprayed before the trees flowered.

Amount used, in percent: Percent attack (1-5 larvae per bud) on an average of 200 bud shoots Untreated 50 .5 0.03% Example 1 0 0.03% Example 2 0 0.02% Compound V 0 In the laboratory, Schmierlause (Pseudoco'ccus citri) on Bryophyllium were treated with the following compounds and degree of success:

Percent effectiveness 0.03% Example 2 78 0.05% Fenitrothion 80 0.02% compound V 24 EXAMPLE 16 Larvae in the second stage, and young females of Aspidiotus hederae, on Arilia were treated with the compound of Example 1 and with Parathion.

Percent effectiveness 0.03% compound 1 84 0.04% Parathion 100 EXAMPLE 17 Thrips tabaci on phlox was treated with the compounds of Examples 1 and 2 and the number of thrips larvae and imagines per 10 stem buds at a time were determined.

Before After treatment 7 days Untreated 142 171 0.03% Compound of Example 1 135 0 0.03% Compound of Example 2 212 0 0.025% Compound V 100 0 EXAMPLE l8 10 May beetles at a time were dipped into a spray solution containing the active substances of Examples 1 and 2 and Parathion and were put on to untreated leaves after drying; the degree of success was determined 24 hours later.

Amount used: Percent mortality Untreated 0 0.00 75% compound of Example 1 100 0.0075 compound of Example 2. 100 0.005% Parathion 100 6 In a feeding experiment on leaves which had been treated with the same spray solutions, the following mortality rates were determined after 24 hours:

Amount used: Mortality Untreated 0 0.015% compound of Example 1 100 0.015% compound of Example 2 100 0.01% Parathion 100 EXAMPLE 19 Merlot vines were sprayed to combat the second generation of grape wickler and the degree of attack, in percent, determined on 3 x 300 grapes.

Attack Efieetivein ness, in

Amount used percent percent Untreated 34 0 03% compound of Example 1 6. 5 81 0.03% compound of Example 2 0. 5 99 0.02% parathion 0 100 EXAMPLE I20 4 X 5 larvae each of the saltmarch caterpillar (Estigmene acrea) in the 3rd stage of development were dipped into the spray solutions and then placed on dried cotton leaves.

The mortality rate was determined after 48 hours.

Amount used: Mortality in percent 5 Untreated 0.02% compound of Example 1 100 0.1% compound of Example 2 0.02% Parathion 90 0.1% carbaryl 60 EXAMPLE 21 Cabbage seedlings had 1 dl. (decilitre) of the spray solutions quoted below poured over them, and cabbage flies placed thereon. The damage and the number of caterpillars was assessed after 1 month.

Total number Proportion Total no. of Amount used of plants damaged caterpillars Untreated 521 49=94% 51 0.03% compound of Ex. 1 40 4=10% 2 0.03% compound of Ex. 2. 48 6=10% 22 0.025% compound V 41 5=12% 1 EXAMPLE 22 An 0.1% acetone solution of ester of Example 1 shows contact eifec-tiver'ress against Drosophila melanogaster both after /2 an hour and after 8 hours. The ester of Example 2 acts in the same way. The same solution was diluted to 0.01%, 0.001% and 0. 0005%. At these dilutions, the contact effect on Musca domestica was still always 100% after 8 hours.

EXAMPLE 23 in which R represents a member selected from the group consisting of lower alkoxy, lower alkylthio, lower alkyl,

lower chloroalkyl, lower bromoalkyl, phenyl and halogen substituted phenyl, wherein halogen is selected from the group consisting of chlorine and bromine, R denotes methyl or ethyl, and X and Y independently represent oxygen or sulfur, together with a suitable carrier.

2. A pesticidal preparation as claimed in claim 1, wherein the active substance is a compound of the formula \ll /P-O 1 0 11 0 3. A pesticidal preparation as claimed in claim 1,

wherein the active substance is a compound of the formula 01 OHaO S CHsO 1 4. A method of treating living plants to protect them from inserts and fungi, which comprises applying to the References Cited UNITED STATES PATENTS 2,599,516 6/1962 Moyle 260964 3,149,143 9/1964 Newallis et a1 260964' 3,356,772 12/1967 Buck ct al 260964 ALBERT T. MEYERS, Primary Examiner J. D. GOLDBERG, Assistant Examiner US. Cl. X.R. 

